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Bustamante was born in coastal Rio de Janeiro and originally had dreams of professional surfing, but began training in Brazilian jiu-jitsu soon after having his first fight when he was 10 years old. Bustamante began officially competing when he was 15 years old, before adding judo, and then began boxing when he was 18. Bustamante is a black belt under the renowned Carlson Gracie. He has won numerous world titles in Brazilian Jiu-Jitsu, which includes the World Championships of Jiu-Jitsu.

Murilo's grappling accomplishments include Championships at the World Class level, as well as appearances at the ADCC World Submission Wrestling Championships. In Brazilian Jiu-Jitsu, he has won The Mundials World Championships in 1999 and has won the Brazilian National Championship 4 times.

In ADCC, he competed at the 88–98 kg in both 1999 and 2000, and the Absolute tournament in 1999. He managed a record of 3–2 with his losses coming by way of points over submission.